3, 3-dialkoxythietane-1, 1-dioxides and their preparation



United States Patent 3,377 358 3,3-DIALKOXYTHlETAlSlE-l,l-DIOXIDES ANDTHEIR PREPARATION James C. Martin, Kingsport, Tenn., assignor to EastmanABSTRACT OF THE DISCLOSURE v The invention relates to3,3-dialkoxy-thietane-l,l-dioxides and their preparation, useful as dyeintermediates and solvents.

This application is continuation of my copending ap- {plication Ser. No.276,161, filed Apr. 29, 1963, now abandoned.

This invention relates to novel organic compounds and more particularlyto 3,3-dialkoxythietane-1,l-dioxides and to a method for preparing them.The compounds of the invention have the general formula:

R2 R al-S02 (RO)2(IJCRB R4 The substituents R, taken singly, are loweralkyl radicals, e.g., methyl, ethyl, propyl, butyl, t butyl, etc., and,taken collectively, represent an alkylene radical as derived from analkylene glycol of 2 to about 8 carbon atoms, which alkylene ra'dicalforms, with the two oxygen atoms and the carbon atom to which the oxygenatoms are attached, a heterocyclic ring having 5 to 8 ring atoms.Examples of such alkylene radicals represented 'by the Rs takencollectively include ethylene, trimethylene, tetramethylene,pentamethylene, and the alkylene radicals derived from branched glycolssuch as 1,3-buty1ene (derived from 1,3- hutanediol) and2,2,4-trimethyl-1,3-pentylene (derived from2,2,4-trimethylphentane-1,3-diol).

R R R and R taken singly, are hydrogen or alkyl radicals of 1 to 8carbon atoms. Said alkyl radicals can be straight or branch chain. Anyone or more of the radicals R R R and R can also be a mononuclear arylradical with or without alkyl substituent's and having up to 8 carbonatoms. R and R taken collectively, and R and R taken collectively, canbe joined lower alkylene radicals which, with the common carbon atom towhich they are attached, form a saturated carbo'cyclic group having 4 to6 ring carbon atoms. Preferred substituents R, R R R and R include thestraight and branched chain lower alkyl radicals such as methyl, ethyl,propyl and butyl.

The method of the invention, by which the novel compounds are prepared,in general comprises combining in an inert solvent an alkyl or arylsulfonyl chloride or bromide of the formula, R R CH-SO X, where X is C1or Br, and a ketene acetal of the formula, R R C= C(OR) in the presenceof a hydrogen halide acceptor, e.g., a tertiary amine. The resultingcycloaddition product is then isolated, eg, by distillation 'orrecrystallization. The reaction can be illustrated by the followingequation:

wherein the substituents R R R and R have the meanings stated above.

As indicated by the formula, R R CHSO X, the sulfonyl halide must haveat least one hydrogen on the carbon atom adjacent to the sulfonyl atom.The sulfonyl chlorides are greatly preferred for economic reasonsalthough for some reactions the bromides can be advantageous. Typicalsulfonyl halides that are suitable include: methanesulfonyl chloride,methanesulfonyl bromide, ethanesulfonyl chloride, Z-propanesulfonylchloride, l-hexane'sulfonyl chloride, S-nonanesulfonyl chloride,diphenylmethane'sulfonyl chloride, etc.

Ketene acetals of the formula R R C=C(OR) which are suitable for theprocess of the invention are disclosed by S. M. McElvain, Chem. Rev.,45, 453 (1949). Examples include ketene dimethyl acetal, ketene diethylacetal, ketene diphenyl acetal, ketene ethylene acetal, dimethylketenedimethyl acetal, dimethylketene ethylene acetal, diphenylketene dimethylacetal, dichloroketene dimethyl acetal, phenylketene dimethyl acetal,cyanoketene diethyl acetal, dicarbomethoxyketene dimethyl acetal, etc.

The process requires the use of a basic material as a hydrogen halideacceptor. Generally I use a tertiary amine for this purpose. Suitablecompounds include: trimethylamine, triethylamine, triethylenediamine,pyridine, quino'line, tetramethylethylene diamine,N,N'-dimethylpiperazine, N,N-dimethylaniline, picoline, lutidine, N-alkyl piperidine's, N-alkyl morpholines, etc.

The process of my invention can be operated at temperatures from about10 to C. or higher. Some of the less reactive ketene acetals andsulfonyl chlorides require temperatures near the upper end of thisrange. Generally, I prefer to use a solvent for the process. Suitablesolvents include those that do not react with the products or thestarting materials. Of particular use are e'thers, such as diethylether, diisopropyl ether, dioxane, tetra'hydrofuran, 1,2-diethoxyethane,etc.

The preferred order of addition of reagents is to mix the solvent,tertiary amine and ketene acetal and to this solution add the sulfonylchloride. Alternate methods can be used and at times are beneficial.Generally the molar ratio of sulfonyl chloride to ketene acetal is 1:1;but other combinations have been used to good advantage. The tertiaryamine is generally employed in excess, ranging from 10% to severalhundred percent. In fact the excess amine can be employed as the solventsince, after the stoichiometric amount of amine has combined with theHCl, the unreacted excess amine is inert.

The following examples illustrate the process and compounds of theinvention.

Example 1 To a stirred solution of 21.0 g. (0.18 mole) of ketenediethylacetal and 35 g. (0.34 mole) of triethylamine in 200 ml. of etherwas slowly added 20.6 g. (0.18 mole) olt methanesulfonyl chloride. Thetemperature was maintained at 15-25 during the addition by use of an icebath. The mixture was filtered to removed the triethy-laminehydrochloride and the filtrate was distilled through a 6-in. Vigreuxcolumn to give 24.8 g. (71%) of 3,3-diethoxythietane-l,l-dioxide, B.P.1l51'16 (0.5 mm.). This material solidified on cooling to a substancemelting at 4849.5.

Analy'sis.Calcd. for C H O S: C, 43.3; H, 7.3; S, 16.5. Found: C, 43.0;H,7.3; S, 16.4. The nuclear mag netic resonance of this compound was incomplete agreement with the structure assigned.

3 Example 2 To a stirred solution of 11.6 g. of (0.1 mole) ofdimethylketene dimethyl acetal and 50.5 g. (0.5 mole) of triethylaminein 100 ml. of diisopropyl ether was slowly added 11.5 g. (0.1 mole) ofmethane sulfonyl chloride. The temperature was maintained at 20-40during the addition by use of an ice bath. The mixture was filtered toremove the triethylamine hydrochloride and the filtrate was distilledthrough a small Vigreux column to give 10.1 g. (51%) of3,3-dimethoxy-2,2-dimethylthietane1,l-dioxide, B.P. 104107 (0.3 mm.).

'Analysis.Calcd. for C H O S: S, 16.5. Found: S,

(CH3) s (01130) To a stirred, refluxing solution of 7.2 g. (.05 mole) of2-pr-opane sulfonyl chloride and 5.6 g. (.05 mole) of triethylenediaminein 100 ml. of tetrahydrofuran was added 4.4 g. (.05 mole) of ketenedimethyl acetal. Refiuxing was continued for 3 hrs. after the addition.The mixture was cooled, filtered and the filtrate was evaporated undervacuum. The infrared spectrum of the residue oil was identical to thatof the product obtained in Example 2 showing this material to be3,3-dimethoxy-2,2- dimethylthiet-ane-1,1-dioxide.

Example 3 Example 4 Under the general conditions of Example 3 thefollowing sulfonyl chlorides and ketene acetals give the 3,3-dialkoxythietane-l, l-dioxides shown:

Other suitable process variables are illustrated as follows:

Example 5 To a stirred, refluxing solution of 21.0 g. (0.18 mole) ofketene diethylacetal and 37.0 g. (0.2 mole) of tributylamine in 100 ml.of dioxane is added a solution of 20.6 g. (0.18 mole) of methanesulfonylchloride in 40 ml. of dioxane over a period of min. Refluxing iscontinued for 1 hr. The reaction mixture is cooled, filtered and thefiltrate distilled to give 3,3-diethoxythietane-1,1- dioxide.

The compounds of the invention are useful as chemical intermediates. Forexample, by heating in dilute aqueous solution of a mineral acid theycan be hydrolyzed to 3- thietanone 1,1-dioxides, as disclosed in mycopending United States application Ser. No. 274,850, filed Apr. 22,1963 entitled 3-Thietanone 1,1-Dioxides. The latter compounds are alsovaluable chemical intermediates. They can be combined with so-calledI.C.I. intermediates to form cyanine dyes useful as photographicspectral sensitizing dyes and with alcohols to form aliphatic alkylsulfonyl esters useful as dye intermediates, all of which is disclosedin said copending application.

' The compounds of the invention are also useful as solvents. Forinstance they will dissolve polyacrylonitrile, a difficult substance todissolve.

The invention has been described in considerable detail with particularreference to certain preferred embodiments thereof, but it will beunderstood that variations and modifications can be effected within thespirit and scope of the invention as described hereinabove, and asdefined in the appended claims.

I claim: 1. A compound of the formula R2 R ]S02 (R0)2( J( |3R wherein:

(a) the substituents R, taken singly, are lower alkyl radicals and,taken collectively, represent an alkylene radical of 2 to 8 carbon atomswhich with the two oxygen atoms to which it is attached and the carbonatom to which the latter are attached, form a heterocyclic ring having 5to 8 ring atoms;

(b) R R R and R taken singly, are selected from the group consisting ofhydrogen, an alkyl radical of up to 8 carbon atoms, and a mononucleararyl radical of up to 8 carbon atoms; and,

(c) R and R taken collectively, and R and R taken collectively, arejoined lower alkylene radicals which with the carbon atom to which theyare attached, form a saturated carbocyclic group having 4 to 6 ringcarbon atoms.

2. The compound according to claim 1 which is 3,3-

diethoxythietane 1,1-dioxide.

3. A compound according to claim 1 which is 3,3-

dimethoxy-2,2-dimethylthietane 1,1-dioxide.

4. The method of producing a compound of the formula I R1OS02 (RO)2(J Rwhich comprises combining a sulfonyl halide of the formula, R R CHSO X,and a ketene acetal of the formula, R R C=C(OR) at a temperature ofabout l0 to C. in an inert solvent and in the presence of a tertiaryamine; wherein:

(a) the substituents R, taken singly, are lower alkyl radicals and,taken collectively, represent an alkylene radical of 2 to about 8 carbonatoms which with the two oxygen atoms to which it is attached and thecarbon atom to which the latter are attached, form a heterocyclic ringhaving 5 to 8 ring atoms;

(b) R R R and R taken singly, are selected from the group consisting ofhydrogen, alkyl radicals of up to 8 carbon atoms, and mononuclear arylradicals up to 8 carbon atoms;

(0) R and R taken collectively, and R and R taken collectively, arejoined lower alkylene radicals which with the carbon atom to which theyare attached, form a saturated carbocyclic group having 4 to 6 carbonatoms; and

((1) X is selected from the group consisting of Cl and 5. A methodaccording to claim 1 of producing 3,3-di'methoXy-2,Z-dimethylthientane-1,l-dioxide which commethane sulfonylchloride with ketene diethylacetal at a temperature from about 1() to100 C. in an inert solvent and in the presence of a tertiary amine.

6. A method according to claim 1 of producing 3,3-dimethoxy-2,2-dimethylthietane-1,1-dioxide which comprises combiningmethane sulfonyl chloride With dimethylketene dimethyl acetal at atemperature from about -10 to 100 C. in an inert solvent and in thepresence of a tertiary amine.

6 7. A method according to claim 1 of producing 3,3-dimethoXy-2,2-dimethy1thietane-1,1-dioxide which comprises combining2-propane sulfonyl chloride with ketene dimethyl acetal at a temperaturefrom about 10 to 5 100 C. in an inert solvent and in the presence of atertiary amine.

References Cited Truce et al.: Jour. Amer. Chem. Soc., vol. 84 (1962),10 pp. 30304.

JAMES A. PATTEN, Primary Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3 ,377,358 April 9 1968 James C. Martin It is hereby certified that errorappears in the above numbered patent requiring correction and that thesaid Letters Patent should read as corrected below.

Column 1 line 43 4-trimethylphentane-l ,3-diol" should read2,2,4-trimethylpentane-l,3-di0l Column 2, line 15, "45" should read 45Column 3, lines 2 to 4, and lines 18 to 21, the right Hand portion ofthe formulas,

each occurrence, should read (CH SO (CH 0) Column 5 line 4 "3,S-dimethoxy-Z ,2-dimethylthientane-l ,ldioxide" should read3,3-diethoxythietane-l,l-dioxide Column 6, line 4, "10" should read l0Signed and sealed this llth day of November 1969.

(SEAL) Attest:

WILLIAM E. SCHUYLER, JR.

EDWARD M.FLETCHER,JR.

Commissioner of Patents Attesting Officer

